-
Biosensors & Bioelectronics Jun 2024An electrochemical (EC) sensor based on metalloporphyrin metal-organic framework (MOF) for the detection of parathion-methyl (PM) has been developed. The prepared...
An electrochemical (EC) sensor based on metalloporphyrin metal-organic framework (MOF) for the detection of parathion-methyl (PM) has been developed. The prepared MOF-525(Fe) exhibits great signal enhancement toward the electrochemical detection of PM owing to its unique structural properties and electrochemical activities. Under optimal experimental conditions, the as-prepared MOF-525(Fe) based EC sensor exhibited excellent PM sensing performance with a wide linear detection range (0.1 μM-100 μM) and low limit of detection (LOD, 1.4 nM). Compared to its corresponding Fe metalloporphyrin (linker), MOF-525(Fe) exhibited a superior sensitivity (28.31 μA cm·μM), which is 3.7 times higher than the sensitivity of FeTCPP linker (7.56 μA cm·μM) towards PM. The improved performance is associated with the high specific surface area and the large pore channels of MOF-525(Fe) facilitating a better interaction between PM and the Fe metalloporphyrin active sites, especially in the lower concentration range. Moreover, a possible affinity of the PM molecules toward Zr clusters may also contribute to the selective enrichment of PM on MOF-525(Fe). This EC sensor further demonstrated high selectivity in the presence of interfering molecules. The recovery results further confirm accurate PM sensing in actual samples, which suggests promising applications for the rapid detection of environmental organophosphates by metalloporphyrin MOFs.
PubMed: 38909444
DOI: 10.1016/j.bios.2024.116515 -
Biomolecules May 2024Olesoxime, a cholesterol derivative with an oxime group, possesses the ability to cross the blood-brain barrier, and has demonstrated excellent safety and tolerability...
Olesoxime, a cholesterol derivative with an oxime group, possesses the ability to cross the blood-brain barrier, and has demonstrated excellent safety and tolerability properties in clinical research. These characteristics indicate it may serve as a centrally active ligand of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE), whose disruption of activity with organophosphate compounds (OP) leads to uncontrolled excitation and potentially life-threatening symptoms. To evaluate olesoxime as a binding ligand and reactivator of human AChE and BChE, we conducted kinetic studies with the active metabolite of insecticide parathion, paraoxon, and the warfare nerve agents sarin, cyclosarin, tabun, and VX. Our results showed that both enzymes possessed a binding affinity for olesoxime in the mid-micromolar range, higher than the antidotes in use (i.e., 2-PAM, HI-6, etc.). While olesoxime showed a weak ability to reactivate AChE, cyclosarin-inhibited BChE was reactivated with an overall reactivation rate constant comparable to that of standard oxime HI-6. Moreover, in combination with the oxime 2-PAM, the reactivation maximum increased by 10-30% for cyclosarin- and sarin-inhibited BChE. Molecular modeling revealed productive interactions between olesoxime and BChE, highlighting olesoxime as a potentially BChE-targeted therapy. Moreover, it might be added to OP poisoning treatment to increase the efficacy of BChE reactivation, and its cholesterol scaffold could provide a basis for the development of novel oxime antidotes.
Topics: Humans; Butyrylcholinesterase; Acetylcholinesterase; Ligands; Oximes; Cholinesterase Reactivators; Cholinesterase Inhibitors; Cholestenones; Kinetics; Sarin; GPI-Linked Proteins; Antidotes; Cholesterol; Organophosphorus Compounds
PubMed: 38785995
DOI: 10.3390/biom14050588 -
Environmental Analysis, Health and... Mar 2024Developing countries like Nigeria are increasingly employing pesticides to boost the productivity of their agriculture and food supply, despite the fact that doing so...
Developing countries like Nigeria are increasingly employing pesticides to boost the productivity of their agriculture and food supply, despite the fact that doing so poses a health risk to the general populace. The purpose of this study was to assess pesticide residue levels in Lagos, Nigeria. A total of 18 samples from three neighbourhood markets were collected, and they were then examined for the presence of organochlorine (Endosulfan I, Pentachlorophenol, Heptachlor epoxide, and Endosulfan II) and organophosphate (Dichlorvos, Dimethoate, Phorate, and methyl parathion) residues. During the pre-treatment, the multi-residue Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS citrate) method with the addition of acetonitrile was used, and then samples were analysed using GC-MS. All of the samples contained dichlorvos, but the orange sample's concentration was below the limit of quantification, making quantification impossible. Dimethoate concentrations were below MRLs except waterleaf sample. With a concentration of 0.043 μg/mL, Waterleaf had the highest quantity of dimethoate in the sample. The findings of this study indicate that in order to safeguard the health of consumers, it is necessary to closely monitor organochlorine and organophosphate use nationwide, along with other related pesticides, and to test for pesticide residues in food products.
PubMed: 38631394
DOI: 10.5620/eaht.2024002 -
Food Chemistry Jul 2024The unreasonable use of organophosphorus pesticides leads to excessive pesticide residues in food, seriously threatening public health, and the potential of...
The unreasonable use of organophosphorus pesticides leads to excessive pesticide residues in food, seriously threatening public health, and the potential of surface-enhanced Raman spectroscopy (SERS) technology, incorporating a metal-organic framework, is substantial for the rapid detection of trace pesticide residues. Here, a novel FeO@NH-MIL-101(Fe)@Ag (FNMA) SERS nanosensor was developed. Results indicated that the FNMA had a high enhancement factor of 1.53 × 10, a low limit of detection (LOD) of 4.55 × 10 M, and a relative standard deviation of 7.73 % for 4-nitrothiophenol, demonstrating its good SERS sensitivity and uniformity, and also possessed good storage stability for one month. In quantifying fenthion and methyl parathion in standard solutions and apple juice in the range of 0.05/0.02-20 mg/L, it showed LODs of 3.02 × 10 mg/L and 1.43 × 10 mg/L, and 0.0407 and 0.0075 mg/L, respectively, demonstrating potentials in ultrasensitive trace detection of pesticides in food.
Topics: Pesticides; Malus; Pesticide Residues; Organophosphorus Compounds; Spectrum Analysis, Raman; Fruit; Magnetic Phenomena; Metal Nanoparticles
PubMed: 38460279
DOI: 10.1016/j.foodchem.2024.138846 -
Environmental Research May 2024Pesticide exposure has been linked to some autoimmune diseases and colorectal cancer, possibly via alteration of gut microbiota or other mechanisms. While pesticides...
BACKGROUND
Pesticide exposure has been linked to some autoimmune diseases and colorectal cancer, possibly via alteration of gut microbiota or other mechanisms. While pesticides have been linked to gut dysbiosis and inflammation in animal models, few epidemiologic studies have examined pesticides in relation to inflammatory bowel disease (IBD).
OBJECTIVES
We evaluated use of pesticides and incident IBD in 68,480 eligible pesticide applicators and spouses enrolled in the Agricultural Health Study.
METHODS
Self-reported IBD cases were identified from follow-up questionnaires between enrollment (1993-1997) and 2022. We evaluated IBD incidence in relation to self-reported ever use of 50 pesticides among applicators and spouses. We also explored associations with intensity-weighted lifetime days (IWLD) of pesticide use among male applicators. Covariate-adjusted hazard ratios (HR) and 95% confidence intervals (CI) were calculated using Cox regression.
RESULTS
We identified 454 IBD cases, including 227 among male applicators. In analyses with applicators and spouses combined, associations were positive (HR > 1.2) for ever vs. never use of five organochlorine insecticides, three organophosphate insecticides, one fungicide, and five herbicides. HRs were highest for dieldrin (HR = 1.59, 95%CI: 1.03, 2.44), toxaphene (HR = 1.61, 95%CI: 1.17, 2.21), parathion (HR = 1.42, 95%CI: 1.03, 1.95), and terbufos (HR = 1.53, 95%CI: 1.19, 1.96). We had limited power in many IWLD of pesticide use analyses and did not find clear evidence of exposure-response trends; however, we observed elevated HRs in all tertiles of IWLD use of terbufos compared to never use (T1 vs. never use HR = 1.52, 95%CI: 1.03, 2.24; T2 vs. never use HR = 1.53, 95%CI: 1.04, 2.26; T3 vs. never use HR = 1.51, 95%CI: 1.03, 2.23).
CONCLUSIONS
Exposure to specific pesticides was associated with elevated hazards of IBD. These findings may have public health importance given the widespread use of pesticides and the limited number of known modifiable environmental risk factors for IBD.
Topics: Humans; Male; Pesticides; Middle Aged; Female; Occupational Exposure; Inflammatory Bowel Diseases; Spouses; Adult; Aged; Farmers; Incidence; Iowa; Agriculture
PubMed: 38354883
DOI: 10.1016/j.envres.2024.118464 -
ACS Omega Dec 2023Exfoliated kaolinite nanosheets (EXK) and their hybridization with β-cyclodextrin (β-CD/EXK) were evaluated as potential-enhanced adsorbents of methyl parathion (MP)...
Advanced Equilibrium Modeling for the Synergetic Effect of β-Cyclodextrin Integration on the Adsorption Efficiency of Methyl Parathion by β-Cyclodextrin/Exfoliated Kaolinite Nanocomposite.
Exfoliated kaolinite nanosheets (EXK) and their hybridization with β-cyclodextrin (β-CD/EXK) were evaluated as potential-enhanced adsorbents of methyl parathion (MP) in synergetic investigations to determine the effects of the different modification procedures. The adsorption behaviors were described on the basis of the energetic steric and energetic factors of the specific advanced equilibrium models (monolayer model of one energy). The functionalization process with β-CD enhanced the adsorption behaviors of MP considerably to 350.6 mg/g in comparison to EXK (291.7 mg/g) and natural kaolinite (K) (244.7 mg/g). The steric studies revealed a remarkable improvement in the quantities of the existing receptors after exfoliation ( = 134.4 mg/g) followed by β-CD hybridization ( = 162.3 mg/g) as compared to K (75.7 mg/g), which was reflected in the determined adsorption capacities of MP. Additionally, each active free site of β-CD/EXK can adsorb about 3 molecules of MP, which occur in a vertical orientation by types of multimolecular mechanisms. The energetic investigations of Gaussian energy (<8.6 kJ/mol) and adsorption energy (<40 kJ/mol) validate the physical adsorption of MP, which might involve the cooperation of dipole bonding forces, van der Waals, and hydrogen bonding. The properties and entropy values, free enthalpy, and intern energy as the investigated thermodynamic functions declared the exothermic and spontaneous behaviors of the MP adsorption.
PubMed: 38144066
DOI: 10.1021/acsomega.3c07088 -
Molecules (Basel, Switzerland) Nov 2023An unprecedented photocatalyst, SmEuSbO, was successfully fabricated in this paper, through a high-temperature solid-state calcination method, which represented its...
An unprecedented photocatalyst, SmEuSbO, was successfully fabricated in this paper, through a high-temperature solid-state calcination method, which represented its first ever synthesis. Additionally, using the solvothermal method, the SmEuSbO/ZnBiSbO heterojunction photocatalyst (SZHP) was fabricated, marking its debut in this study. XRD analysis confirmed that both SmEuSbO and ZnBiSbO exhibited pyrochlore-type crystal structures with a cubic lattice, belonging to the Fd3m space group. The crystal cell parameter was determined to be 10.5682 Å or 10.2943 Å for SmEuSbO or ZnBiSbO, respectively. The band gap width measured for SmEuSbO or ZnBiSbO was 2.73 eV or 2.61 eV, respectively. Under visible light irradiation for 150 min (VLTI-150 min), SZHP exhibited remarkable photocatalytic activity, achieving 100% removal of parathion methyl (PM) concentration and 99.45% removal of total organic carbon (TOC) concentration. The kinetic constant () for PM degradation and visible light illumination treatment was determined to be 0.0206 min, with a similar constant of 0.0202 min observed for TOC degradation. Remarkably, SZHP exhibited superior PM removal rates compared with SmEuSbO, ZnBiSbO, or N-doped TiO photocatalyst, accompanied by removal rates 1.09 times, 1.20 times, or 2.38 times higher, respectively. Furthermore, the study investigated the oxidizing capability of free radicals through the use of trapping agents. The results showed that hydroxyl radicals had the strongest oxidative capability, followed by superoxide anions and holes. These findings provide a solid scientific foundation for future research and development of efficient heterojunction compound catalysts.
PubMed: 38067453
DOI: 10.3390/molecules28237722 -
Toxics Sep 2023New approach methods (NAMs) can reduce the need for chronic animal studies. Here, we apply benchmark dose (concentration) (BMD(C))-response modeling to transcriptomic...
New approach methods (NAMs) can reduce the need for chronic animal studies. Here, we apply benchmark dose (concentration) (BMD(C))-response modeling to transcriptomic changes in the liver of mice and in fathead minnow larvae after short-term exposures (7 days and 1 day, respectively) to several dose/concentrations of three organophosphate pesticides (OPPs): fenthion, methidathion, and parathion. The mouse liver transcriptional points of departure (TPODs) for fenthion, methidathion, and parathion were 0.009, 0.093, and 0.046 mg/Kg-bw/day, while the fathead minnow larva TPODs were 0.007, 0.115, and 0.046 mg/L, respectively. The TPODs were consistent across both species and reflected the relative potencies from traditional chronic toxicity studies with fenthion identified as the most potent. Moreover, the mouse liver TPODs were more sensitive than or within a 10-fold difference from the chronic apical points of departure (APODs) for mammals, while the fathead minnow larva TPODs were within an 18-fold difference from the chronic APODs for fish species. Short-term exposure to OPPs significantly impacted acetylcholinesterase mRNA abundance (FDR -value <0.05, |fold change| ≥2) and canonical pathways (IPA, -value <0.05) associated with organism death and neurological/immune dysfunctions, indicating the conservation of key events related to OPP toxicity. Together, these results build confidence in using short-term, molecular-based assays for the characterization of chemical toxicity and risk, thereby reducing reliance on chronic animal studies.
PubMed: 37888672
DOI: 10.3390/toxics11100820 -
International Journal of Analytical... 2023Antibiotics and pesticides are widespread in most rivers and lakes due to the overuse of antibiotics and pesticides, but there are few methods for simultaneous analysis...
Antibiotics and pesticides are widespread in most rivers and lakes due to the overuse of antibiotics and pesticides, but there are few methods for simultaneous analysis of antibiotics and pesticides in aquatic environments. To address this knowledge gap, a concise and sensitive analytical method is proposed in which three classes of human and veterinary drugs (sulfonamides, macrolides, and hormones) and two classes of pesticides (organophosphorus and neonicotinoids) are simultaneously extracted and determined in surface water. The solid-phase extraction column with Cleanert PEP-2 was preconditioned sequentially with 6 mL of methanol, ultrapure water, and citric acid buffer (pH 3.0) each for simultaneous extraction and further purification. The forty-seven target analytes were analysed by LC-MS/MS in positive and negative ion modes. The LC separation was performed using a Sigma-Aldrich C column with 0.1% formic acid in water and acetonitrile as a gradient eluting mobile phase in positive ion mode. The internal standard method was used to overcome the inevitable matrix effects in LC-MS/MS analysis. The matrix effects of most target analytes were in the range of 27-151%. The recoveries of forty analytes in the three concentrations (10, 50, and 100 ng L) of surface water spiked samples ranged from 41 to 127%. The method quantitative limits of the analytes were in the range of 0.40-5.49 ng L. Application of the method to analyze samples in the eight runoff outlets of the Pearl River Delta showed that some antibiotics and pesticides were detected, and the concentration of parathion was as high as 154 ng L. A powerful tool for quickly and efficiently screening for contaminants in surface water has been presented.
PubMed: 37877028
DOI: 10.1155/2023/6350669 -
Foods (Basel, Switzerland) Sep 2023In modern agricultural practices, organophosphorus pesticides or insecticides (OPs) are regularly used to restrain pests. Their limits are closely monitored since their...
A Multi-Enzyme Cascade Response for the Colorimetric Recognition of Organophosphorus Pesticides Utilizing Core-Shell Pd@Pt Nanoparticles with High Peroxidase-like Activity.
In modern agricultural practices, organophosphorus pesticides or insecticides (OPs) are regularly used to restrain pests. Their limits are closely monitored since their residual hinders the capability of acetylcholinesterase (AChE) and brings out a threatening accumulation of the neurotransmitter acetylcholine (ACh), which affects human well-being. Therefore, spotting OPs in food and the environment is compulsory to prevent human health. Several techniques are available to identify OPs but encounter shortcomings like time-consuming, operating costs, and slow results achievement, which calls for further solutions. Herein, we present a rapid colorimetric sensor for quantifying OPs in foods using TMB as a substrate, a multi-enzyme cascade system, and the synergistic property of core-shell Palladinum@Platinum (Pd@Pt) nanoparticles. The multi-enzyme cascade response framework is a straightforward and effective strategy for OPs recognition and can resolve the previously mentioned concerns. Numerous OPs, including Carbofuran, Malathion, Parathion, Phoxim, Rojor, and Phosmet, were successfully quantified at different concentrations. The cascade method established using Pd@Pt had a simple and easy operation, a lower detection limit range of (1-2.5 ng/mL), and a short detection time of about 50 min. With an R value of over 0.93, OPs showed a linear range of 10-200 ng/mL, portraying its achievement in quantifying pesticide residue. Lastly, the approach was utilized in food samples and recovered more than 80% of the residual OPs.
PubMed: 37685251
DOI: 10.3390/foods12173319